Process for breaking petroleum emulsions



Patented July 18, 1944 PROCESS FOR BREAKINGJETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Ma, assignors to Petrolite Corporation, Ltd, Wilmington, Del., a corporation of Delaware No Drawing. Application June 15, 1942, Serial No. 447,160

8 Claims. (Cl. 252-341) This invention relates primarily to the resolu tlon of petroleum emulsions. The main object of our invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type, that are commonly re- If treated with an oxyalkylating agent, and momentarily consideration will be limited to an oxyethylating agent, one may obtain an oxyethylated glycerol of the following formula type:

c IE ferred to'as cut oil, roily oil," emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brlnes dispersed in a (canons! more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

' Another object is to provide an economical and rapid process for separating emulsions which'have in which the value of n may vary from 3 to 10 and all the values of u need not be identical. If a polybasic carboxy acid be indicated by the formula:

been prepared under controlled conditions from 0001 mineral oil, such as crude petroleum and rela- -0 0 tively soft waters or weak brines Controlled COOH emulsification and subsequent demulsiflcation under the'condltions just mentioned is of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

We have discovered that if one oxyalkylates glycerol so as to introduce at least'three oxyallr'yl- (cimolboocmco OH) w one radicals for each hydroxyl group, and if the I camorwmmha product so obtained is reacted with a polybasic (C H o) H carboxy acid having not over eight carbon atoms, and in such a manner as to yield a fractional ester, due to the presence of at least one free carboxyl radical, one can then esterify said acidic material or intermediate product with at least one in which n" has the value of one or two. Simithen the compound may be indicated by the following formula:

mole of an alcoholic compound of the type herein (CIHAO);,OOCR(COOH) described to give a variety of new compositions of matter which are emcient demulsiflers for crude oil emulsions. (CzHlO)-'H The compoupds herem described that are used Likewise, if three moles of a polybasic acid are as the demulsifier of our process, may be pro- 5 duced in any suitable manner, but are usually manufactured by following one of two generalprocedures. In one of said procedures the oxyalkylated glycerol, which is, in essence, a polyhydric alcohol, is reacted with a polybasic acid, so as to give an acidic, material or intermediate product, which, in turn, is reacted with an alcoholic body of the kind hereinafter described. and momentarily indicated by the formula. RuIOHm. Generically, the alcoholic body herein contemplated may be considered a member of the class in which m may vary from 1 to 10,- although the specific significance of m in the present instance will be hereinafter indicated. The second procedure is to react an alcohol of the formula type R1(OH) m.

' with a polybasic acid so as to produce an inter mediate product, and then react said intermediate product or fractional ester with the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

or more moles of an alcohol of the kind previously described in a generic sense as R1(OH) m, then obviously, one may obtain a material of the type indicated by the following formula:

[(OmonaoocR(000H).w]= caH or -ucifllofi' h in which :cis o, 1' or 2,- is 0, 1 or 2, and 21$ 1, 2 or 3, and :c is 0 or 1, and y is 1 or2 It has been previously stated that compounds l of the type herein contemplated may be obtained CHFOHJ by oxyalkylating agents, without being limited to OH ethylene oxide. Suitable oxyalkylating agents a polymer of ethylene glycol. The term -mer" is frequently used to indicate the polymercluded, strictly speaking, by the unitary strucboxyllc hydrogen atom appears, it maybe re placed by metaLan ammonium radical, or substituted. ammonium radical, or by an organic group derived from an alcohol, such as an ali-' phatic alcohol, an aralkyl alcohol, or an alicyclic alcohol. It may also be converted into an amide,

including a polyaminoamide; Thus, the preceding formula may be rewritten in its broader scope, as follows:

(cooao. in which n replaces the numbers 2, 3 or 4, Z

above formula, and hereafter for convenience, R1 is intended to include any hydroiwl group's thatremain.

' If the compounds herein contemplated are obtained under usual conditions, at the lowest temperatures, then the monomeric form ismost. likely to result. r The production of the compounds herein contemplated is the result. of one or more esteriflcation steps. As is well known, esterification pros5 cedures can; be carried out in various manners, but generally speaking, esteriflcations can be ca i ried out at thelowest feasible temperatures by using one of-several procedures. One procedureis to pass an inert dried gas through the mass 4 to beesteriiied, and 'havepresent. at the same time a small amount of a catalyst, such as dried HCl gas, a dried sulfonic acid, or the like. Anotherand better procedure, in many instances, is to employ the vapors of a suitable liquid, so as to remove any water formed and condense both the vapors of the liquid employed and the water in such a manner as to trap out the water and return the liquid to the reacting vessel.

This procedure is commonly employed in the 50 arts, and for convenience, reference is. made to U.-- 8. Patent 'No. 2,264,759, dated December 2,

1941, to Paul C. Jones.

Referringagain to the last two formulas indicating the compounds under consideration, it

can be readily understood that such compounds, in numerous instances, have the property of polyfunctionality. In view of this fact, where there is at least one residual carboxyl and at' least one residual hydroxyl, one would expect that under suitable conditions, 'instead of obtaining the monomeric compounds indicated, one would in reality obtaima polymer in the sense.-

.for example, that polyethylene glycols represent ized product derived from a monomer in which the polymer has thesame identical composition as-the'monomer, In the present instance, however, polymerization inyolves'the splitting and-m loss, of water, so that the-process is essentially self-esterification, Thus, strictly speaking, the polymeric compounds are' not absolutely polymers of the monomeric compounds, but since,

for all practical' purposes, they can be so indi- 70 poly- .5

cated; and since such practice is common in the so adopted here. pended claims to polymers is intended to include the self-'esteriflcation products of the monomeric compounds;

In view of what has been said, and in view of the recognized hydrophile properties of the recurring oxyalkylene linkages, particularly the oxyethylene linkage, it is apparent that the materials herein contemplated may vary from compounds which are clearly water-soluble through self-emulsifying oils, to materials which are balsam-like and sub-resinous. or semi resinous in nature. The compounds may vary from monomers to polymers, in which the unitary structure appears a number of times, for instance, 10 or 12 times. It is to be noted that true resins, i. e., truly insoluble materials of a hard plasticnature, are not herein included. In other words, the polymerized compounds are soluble to a fairly definite extent, for instance, at least 5% in some solvents, such as water, alcohol, benne, dichloroe l ether, acetone, cres lic acid, includes the acidic hydrogen atom itself. In the ZS: thy y ferred to as an A resin, or a B resin, as distinguished from a C resin, which -is a highly infusible, insoluble resin (see Ellis, Chemistry of SyntheticResins (1935), pages 862, et. seq).

Reviewing the form as presented, it is obvious that one may obtain compounds within the scope disclosed, which contain neither a free hydroxyl nor a free carboxyl group, and one-may also obtain a compound of the type in which there is present at least one freecarboxyl, or at least cine free hydroxyl, or both. The word polar has sometimes been used in'the arts in this particular sense to indicate the presence of at least one free hydroxyl group, or at least, one free carboxyl group, or both. In the case of the free carboxyl group, the carboxylic hydrogen contemplated in the present instance may be de-- rived from polyhydroxylated compounds having more than three hydroxyl groups. For instance, they may be derived from acyclic diglyoerol, triglycerol, tetraglycerol, mixed polyglycerols, mannitol, sorbitol, various hexitols, dulcitol, pentaerythritol, sorbitan, mannitan, dipentaerythritol mono-ether, and 6ther similar compounds. Such part cular typesinwhich higher hydroxylated materials are subjected to oxyalkylation and then employed in the same manner as 'oxyalkylated glycerol, is employed in the present instance, are not contemplated in this speciilo case, although attention'is directed to the same.

Reference is also made to other oxyalkylated compounds which may be used as reactants to replace oxyalkylated glycerol, or oxyalkylated ethylene glycol, which latter reactant is described in a co-pending applicationhereinafterreferred to. The reactants thus contemplated include the type in which there is an amino or amido nitrogen atom, particularly, when present in a low molal type of compound prior to oxyalkylation, reference being made to polyhydroxylated materials, including those having two or three hydroxyl groups, as well as those having more than three hydroxyl groups. For instance, the oxyalkylated derivatives, particularly the oxyethylated derivatives of ethyldiethanola-mine, bis(hydroxyethyDacetamide, the acetamide of tris(hydroxymethyl) aminomethane, tetrahydroxyethylated ethylene diamine, etc. Compounds may also be derived from cyclic diglycerol and the like.

Furthermore; for convenience, attention is directed to a somewhat similar class of materials which are described in our co-pending application Serial No. 401,376, filed July '1, 1941. Said co-pending application involves the use of the same type of alcoholic bodies for reactants, but is limited, among other things, to the compounds which are essentially symmetrical in nature, for instance, involving the introducing of two alcoholic residues, whereas, in the present instance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to the type having not more than eight carbon atoms, for example, oxalic, malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly, one may employ acids such as fumaric, glutaconic, and various others, such as citric, malic, tartaric, and the like. The selection of the particular tribasic or dibasic acid employed, is usually concerned largely with the convenience of manufacture of the finished ester, and also the price of the reactants. Generally speaking, phthalic acid or anhydride tends to produce resinous materials, and greater care must be employed if the ultimate or final product be of a sub-resinous type. Specifically, the preferred type of polybasic acid is such as to contain six carbon atoms or less. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of esterified product, although polymerization may be stimulated. Oxalic acid may be comparatively cheap, but it decomposes readily at slightly above the boiling point of water. For this reason it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater ease than the acid itself. For this reason, maleic anhydride is particularly adaptable, and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis. Succinic acid or the anhydride has many attractive qualities of maleic anhydride, and this is also true of adipic acid. For'purposes of brevity, the bulk of the examples, hereinafter illustrated, will refer to the use of maieic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, reference is made to derivatives obtained by oxyethylation, although, as previously pointed out, other oxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants is concerned, it is our preference to employ those in which approximately 15 to 24 oxyethylene groups have been introduced into a single glycerol molecule. This means that approximately five to eight oxyethylene radicals hav been introduced for each original hydroxy1 group.

The oxyalkylation of glycerol .is a well known procedure (see Example 11 of German Patent No.'605,9'73, dated November 22, 1934, to I. G. Farbenindustrie Akt. Ges). The procedure indicated in the following three examples is substangravity of 1.383.; lyst. The ethylene oxide is added in relatively tially identical with that outlined in said aforementioned German patent,

OXYETHYLA'IED Gnxcnxor. Example 1 184 pounds of glycero1 is mixed with /2%, by weight, of caustic soda solution having a specific The caustic soda acts as a catasmall amounts, for instance, about 44 pounds at a time. The temperature employed is from 150- 180 C. Generally speaking, the gauge pressure during the operation approximates 200 pounds at the maximum, and when reaction is complete, drops to zero, due to complete absorption of the ethylene oxide. When all the ethylene oxide has been absorbed and the reactants cooled, a second small portion, for instance, 44 more "pounds of ethylene oxide, are added and the procedure repeated until the desired ratio of 15 pound moles of ethylene oxide to one pound mole of glycerol is obtained. This represents660 pounds of ethylene oxide for 92 pounds of glycerol.

QXYETHYLATED GLYCEROL Example 2 OXYETHYLATED Gmzcsaor. Example '3 The same procedure is followed as in the two previous examples, except that the ratio of ethylene oxide to glycerol is increased to 21 to one.

OXYETHYLATED GLYCEROL MALEATE Example 1 OXYETHYLATED GLYCEROL MALEATE Example 2 The same procedure is followed as in the preceding example, except that two moles of maleic anhydride are employed so as to obtain the dimaleate instead of the monomaleate.

OxYE'rHYLA'ran' GLYCEROL MALEATE Example 3 The same procedure'is followed as in the two preceding examples, except that three moles of maleic anhydride are employed so as to obtain the trimaleate.

OXYETHYLATED GLYCERQL Marmara Example 4 OXYETHYLATED Grxoaaor. MALrA'ra Example 5 The same procedure is employed as in the preceiing examples, except that oxyethylated lyof oxyethylated glycerol (1" iHAO Ca OHCIHiN C:H4O C211 OgHrO (3:114

0110 aHtN NCaHiOH NT CIIHLO C2 6 OHC2H4 C2H4OH NCaHiO CH2CHOHCH2OCzHiN NCzHaO CH2CHOHCH2OCzH4N OHCzH-s CZHtOH T OHCaHl OHCtHA OHCzHl C2114 NCzHlO CzHlN O In the above table, it is understood that where the radical C2H4 occurs, it may be,replaced by any other suitable radical, such as a CaHe, C4Hs radical, etc. Furthermore, it may be replaced by a residue from a cyclohexyl radical, or a residue from a benzyl radical or the like. Similarly, where the glycerol radical appears, a homolog may be substituted instead, as, for example, beta-methyl glycerol or the tetrahydroxyl derivative thereof. It is unnecessary to differentiate between isomeric forms; and in some instances, one mayhave polymeric forms containing a large number of residues derived from polyhydric alcohols or hydroxyamines, and of such a kind that there are present perhaps20, 30, 40, or even 50 residues from the parent material or materials which contribute to the formation of the final OHCaHl OHCnHA molecule. Continuous etherization is considered as being polymerization, for purposes of convenience. Such polymers may be considered'a tion of two moles of diethanolamine so as to prorepetition of the monomer, taken any convenient number of time'sfor instance, two to twenty times. It is also to be noted that the molecule may be joined by more than one ether linkage in parallel.

Similarly, morpholine or ethanol morpholine may be employed. Morpholine may be considered as contributing the basic amino nitrogen atom. In each and every instance the intermediate compound or reactant employed in As previously stated, phenyl diethanolamine or similar compounds may enter into the final molecule.

As to the manufacture of such intermediate compounds, which are used as reactants to produce the new composition of matter employed as the demulsifier of our process, one need only point out that some of them are well known compositions of matter. Others can be produced, if desired, in the same manner employed to produce those which are well known. One method of producing such compounds is to heat the desired products under suitable conditions, so as to cause dehydration to take place. Another method is to treat the selected amine with a product such as an alkylene oxide, including ethylene oxide, or with a product such as glycidol. Other methods involving dehydration in the pres ence of an acidic agent, for instance, dehydraduce the other type compound instead of morpholine, may be employed. It is possible that some of the types indicated above, like other organic compounds, are diilicult to prepare, but their derivatives can be prepared more readily. In other words, since an acylated product is de sired, it is feasible, in some instances, to prepare the acylated product by uniting a partially esterifled polyhydric alcohol with a partially esterifled alkalolamine, or by use of an equivalent method. This particular method of producing the desired type of chemical compound or intermediate reactant employed in the manufacture of our new composition of matter or new demul-e sifier, will 'be discussed subsequently.

Attention is directed to the co-pending application for patent, Serial No. 273,278, of Melvin De Groote and Bernhard Keiser, filed May 13,

1939, now U. S. Patent No. 2,293,494, dated August 18, 1942. This particular co-pending application teaches a convenient method for making some of the compounds or intermediate reactants of the kind previously indicated. The said method involves essentially the conversion of an ethanolamine or the like, such as triethanolamine, into a monoor dialcoholate, and the reaction of the alcoholate with a halohydrin, such as glycerol chlorhydrin or glycerol dichlorhydrin. The alcohodittes may be indicated by the following form ae:

CSHAONB CIHAOK N-CsHiOH N-CzHaOH CIKlOH ClHAOH Such alcoholates react so as to liberate the alkali metal halide, such as sodium chloride or potassium chloride. Said co-pending application illustrates, for example, the manufacture of materials of the following type by means of such reaction:

are derivable which are characterized by the presence of an acyl radical obtained i'romvacids having either less than 8 carbon atoms, or, more ethers by use ot'theacylated alcoholate derived by utilization of metallic sodium or potassium or.

the like. In such compo rids the acylradical is attached directly to the ertiary amine residue ,or radical. However, if one employsan esterifledchlorhydrin, i. .e., the chlorhydrin derived from n on .n"

are c-o-ooc-a n n n in. which R.CO is t e acyl' radical derived from RCOO H, which rep esents an acid of the kind previously described By employing such acylated halohydrin or chlorhyiirin, one can use reactants which include reactions of the following droxy aminoether is .taken verbatim from said co-pending application Serial No. 273,278 now- U. S. Patent No. 2,293,494, dated'August18, 1942:

, 100f pounds 01 commercial triethanolamine 45 containing 2 monoetl'ianolan'iine and diethanolamine, are treated'with 135 pounds of a I 60% solution oi caustic soda (i. e., 80% pounds .NaOI-I dissolved in 53 pounds of water) so as to yield a pasty or semi-solid mass containing sub- 60 stantially no freeor relatively little free. alkali.

The wet mass is then reacted with extreme care,.as

previously noted, with commercial glycerol mono- 'chlcrhydrin- After completion of reaction, the

sodium chloride formed is separated by filtration and hydraulic pressure. The 1 product represents a compound of technical purity and has the following composition:

In the hereto appended cla'ims vno reference is made to the fact that the. alcoholate ise'mployed in substantial absence of alkali, because it deemed unnecessary to indicate that this con tionis the most desirable. The objection to an excess oi alkali is .the destruction of the chlorhydrin and the formation oi a polyhydric alco hol or the like, which appears in the completed product. Naturally, there is no objection to small amounts of excess alkali whose significance is not appreciable. It is to be noted in the claims can only be conducted in] vthe absence of free alkali." f The following example tor preparing-a hyt is to be noted that the chlorhydrin involved may of itself be'acylated, and thus compounds;

that no reference is mane to separation of the alcoholate from water, excess alkali, -unreacted amine, 'etc., which may be present, although, as I previously indicated, such separatory procedure 6 may be followed, if desired." 4 7 Having prepared a hydroxyaminoether o! the kindpreviously described, the second step inthe. manufacture of the intermediate compound employed as a reactant is to acylatev such product 9 so as to introduce an acyl radical derived irom a detergent-forming monocarboxy acid. For purposes oiconvenience, such monocarboxy' acid may be indicated by the formula R'.COOI-Iand the acyl group by RZCO. It has already been 15 indicated that acyla'tion may be conducted by use of the acid itselfjor by use of any suitable compound containing the acyl radical in labile form. Attention is directed to U., 3. Patents Nos. 2,154,422 and 2,154,423, to De Groote, Keiser and Blair, both dated April '18, 1939. Both of said paten s are concerned with. products derived by es 7 cation between intermediate amines con-. taining an alcoholic hydroxy group and phthalic anhydride. It is necessarydn the instances described. in said patents that an alcoholic hydroxyl radical be present in reaction with-phthalic anhydride. Insofar that the 'acylated aminoethers herein contemplated as reactants. iorthe manu-. facture of demulsii'ying agents must be esteriiled with maleic anhydride or the like, it is apparent that an alcoholic hydroxyl radical need be present, and that acyl radicals mustb'e introduced. so that there is .a' residual hydroxyl radical attached either toa hydrocarbon radical, or to an acylradical, such as hydroxyl radical which is part 0! aricinoleyl radical. Furthermore, it is apparent thatyeven when 'acylation ,is accomplished 'with an acidhaving no hydroxyl radicals, for instance,- stearic acid oleic' acid, naphthenic 4 acid, or the like;then, in that event, one must 'acylate a hydroxy aminoether-havinamore than one free hydroxyl. radical. A person skilled in the art will readily understand how to employ .the methods and compounds described in said two aforementioned patents to prepare acylated derivatives from hydroxy aminoethers of the kind above described and the-selected detergent-dorming monocarboxy acid compound. a v Said patents indicate ;'the following amines which may .be employed: diethanolamine, monoethanolamine, ethyl ethanolamine, methyl eth-' anolamine, 'propanolamine, -'dipropanolamine,' propyl propanolamine; cyclohenanolamine, dicyclohexanolamine, cyclohexylethanolamine, cyclehexyl propanolamine, benzyl ethanolamina'benzyl propano'lamine; pentanolamine, hexanolamine, octyl eihandlamine, octadecyl, ethanol-- amine, cyclohe anol ethanolamine; methanol-- amine, diethanolalkylamines', such as diethanol .ethylamine, ,diethanol, propylamine; diethanol methylamine, tripropanolamine, dipropanol methylamine, cyclohekanol 'diethanolamine dicyclohexanol ethanolamine, cyclohexyl diethans olamine, dicyclohexyl ethanolamine, dicyclohexo5 anol ethylamine, benzyl diethanolamine, dibenzyl -ethanolamine, benzyl dipropanolamine, tripen-' olamine,. oc tadecyl diethanolamii'ie, polyethanol amine, mono-, diand trig-1ycery1amine,etc. 7 I Attention is also directedto the two aioremen: tioned. patents to the extent that they disclose" and describe various glycerylamines and the' method of manufacturing the same. Such meth- 1' cos obviously are applicable to derivatives ot the kind previously mentioned, such as beta methyltanolamine, trihexanolamine,l ethyl h l l ethanw.

- droxyl' radical has aesa'zos glycerol, beta 'propyl glycerol, beta ethyl glycerol, etc., as Well as derivatives of the tetrahydroxyl compounds obtainable therefrom- It has been previously pointed out that the chemical compounds employed as intermediates or as reactants for the production of the comp sition of matter used as the demulsifier of our process, need not necessarily be manufactured by first, preparing the hydroxyamino-ether, and subsequently acylating the same. As a matter of fact, in many instances it is more convenient to acylate the desired polyhydric alcohol or the desired hydrcxyamine, and then combine the two acylated molecules or acylate on type of compound and combine with the unacylated molecule or the other type. Indeed, an examination of what has been said previously and an examin ation of the method suggested hereinafter, indicates that one can proceed to produce a compound in which the acylated radical derived from the detergent-forming radical is produced at whatever point is desired. In other words, it may be introduced only in one or more hydroxyamino residues which are present; or the acyl radical may be introduced only in one or more polyhydric alcohol residues which are present; or it may be introduced both into the hydroxyamino residues which are present and into the polyhydric alcohol residue which is present. As previously pointed out, if desired, the acyl radical may be introduced more than once into the same hydroxyamino residue, or into the polyhydric alcohol residue, provided there are available 'suflicient alcoholic hydroxyls for such combination.

Acylation, of course, is identical with esterification for the purpose of the present description. In other words, instead of replacing the hydrogen atom of a hydroxyl group by an acyl radical, one can assume that the complete bybeen replaced by an oxyacyl radical; i. e., a fatty acid radical; and thus, the product may be referred to as esterified. Using such'nomenclature, one can refer to an alkanolamine as being particularly esterified with a selected detergentdorming monocarboxy acid or a polyhydric alcohol as being partially esterifled. The manufacture of partially esterified alcohols,

such as superglycerinated fats, is well known; and such compounds have considerable utility in the arts. Needless to say, the same method employed for producing superglycerinated fats may be employed in connection with any polyhydric alcohol and may be employed in connection with other acids instead of fatty acids, for instance, the other non-fatty detergent-forming monocarboxy acidsgsuch as abietic acid, naphthenic acid,

and the like. In view of this fact, no description is. necessary as to the method of preparing partially esterified polyhydric alcohols from detergent-forming acids of the kind described. Furthermore, no description is necessary as to the method of preparing partially esterified alkanolamines, in view of what has been said previously, and particularly in view of the complete description of equivalent acylatlon procedure,'which appears in theaforementioned United States Patents Nos. 2,154,422 and 2,154,423.

Reference is made to U. S. Patent No. 2,228,989, of Melvin De Groote, Bernhard Kaiser, and

Charles M. Blair, Jr., dated January 14, 1941.

Said patent describes compounds obtainable by a method which comprises heating a partially esterified tertiary-alkanolamine with a. polyhydric alcohol to a temperature in excess of 100 C. for a period of time suflicient to cause condensation with elimination of water and the production of an etherealreactlon product. Although said pat-- out is concerned largely with derivatives of fatty acids, needless to say, the same procedure may be applied to comparable compounds derived from naphthenic acid or abietic acid or the like. This is also true in regard to the preparation of subsequent Examples 4-10, inclusive. The following three examples appear in said patent.

Example 1 (Example 1 of the patent) .Cornmercial triethanolamine and cocoanut oil, in the proportions of 1 mole of cocoanut oil to 3 moles of triethanolamine are heated to a temperature between about C. and C. for about two hours. The resulting product consists mainly of the monofatty acid ester of triethanolamine, with minor proportions of the di-fatty acid ester, the tri-fatty acid ester, glycerin, etc. To this reaction product is added somewhat more than 2 moles of glycerin, and the resulting mixture is heated to a temperature between about 160 C. and 180 C. for about two days. If desired, a current of dry nitrogen or other inert ga may be passed through to speed up the reaction. Condensation occurs between the fatty acid ester of the tri-ethanolamine, and the glycerin, with the production of ethereal reaction products, such as the dihydroxypropyl ether of the mono-fatty acid ester of triethanolamine and other more complex ethereal reaction products."

Example 2 (Example 2 of the patent).--Triglycerylamine (tri di-hydroxy-propylamine) and castor oil are reacted in the proportions of 3 moles of castor oil to 2 moles of triglycerylamine, with the production of a product consisting predominantly of the di-ricinoleic acid ester of the triglycerylamine; The resulting mixture is further heated for a period of about two days, with condensation between the glycerin and the diricinoleic acid ester of the triglycerylamine, and the production of corresponding ethereal condensation products.

Example 3 (Example 3 of the patent) .-Blown rapeseed oil and diethanolet-hyla'mine, in the molecular proportions of 3 moles of the amine to 1 mole of the oil are heated togethercto a temperature between about 150 C. and 180 C. for about two hours, with the production of a reaction product containing a large proportion of the mono-ester of the diethanolethylamine, together with unreacted starting material, glycerin, etc. Something in excess of two moles of glycerin are added to the reaction mixture, and the resulting product is heated to about 150 C. to 180 C. for about two days, with the production of ethercal. reaction products of glycerin and the monoester of the diethanolethylamine."

Similarly, attention is called to the U. S. Patent No. 2,228,987, of Melvin De Groote, Bernhard Keiser and Charles M. Blair, Jr., dated January 14, 1941. Said patent describes compounds of the kind obtainable by a method which comprises heating the triglyceride, a tertiary alkanolamine having'more than one alcoholic hydroxyl radical, and a polyhydric alcohol, to a temperature in excess of 100 C. for a period of time suflicient to cause alcoholysis of a triglyceride and condensation between the resulting partially esterified alkanolamine, and partially esterifled glycerine. The following examples appear in said patent:

Example 4 (Example 1 of the patent) .-Commercial tricthanolamine, cocoanut oil and glycerin in the proportions of one mole of cocoanut oil to three moles of triethanolamine and at least one mole of glycerin are heated to a temperature or between about 150 and 180 for a period about arty hours. If desired, a urrent of dry nitrogen may be passed through hereaction mixture.

The resulting product contains a substantial and preponderating amount of the ether resulting from the condensation of the mono-fatty acid ester of triethanolamine and the monoand difatty acid ester of glycerin, shown in the'following formula:

nooocini -c,HiooHr-c,11i(0n)(000R) 1100,11 offlwhich R represents the long carbon linked chain of the cocoanut oil fatty acids."

Example (Esample 2'0! the patent).-Triglycerylamine (tri-dihydroxy-propylamine) and I castor oil are reacted in the proportions of three moles of castor oil to two moles of triglycerylamine, for a period'of about two hours at a temperature of around 150 to 180? C. To the prodnot so produced, which consists predominantly of the diricinoleic acid ester of the'triglycerylamine,

is tadded about 50% of the monon'cinoleic acid es er of glycerin, and the resulting mixture is heated to about 150 tog180 C. for about two days, with the production of mixed ethers of the di-v ricinoleic acid "ester of triglycerylamine \and the monoricinoleic acid ester of formula: I

(RG00) (on)ciHi0--cHt(oM) -1-I[cim(oMmi in which two of the Ms represent the acyl group corresponding to ricinoleic acid and the other three represent'hydrogen, .and in which R represents the carbon linked chain characteristic of ricinoleic acid.

Exampleb (Example 3 of the patent) .-Paim kernel oil and diethanolethyiamine, in' the molecular proportions of three moles of the amine to one mole of the palm kernel oil are heated to- 'getherwith one mole of a polyglycerol to a temperature between about 150 and 180 C. for'about two dayswith the production of a reactioiflirodtogether with more complex ethereal derivatives of the amineand the monoglyceride.-

, Example 8 (Example 5 of the patent) Com mercial triethanolamine, a fatty oil and ethylene glycol in the molecular proportions of two moles of the amine to/onemole of the oil to one mole oi the ethylene glycol are between about150. and 180 with'the production or areaction product con monoester, of triethanolamine with the corresponding mono-glyceride and the ether of the monoester of triethanolamine with the monoester of ethylene glycol.

glycerin, of the type e diethanol'ethylamine ester and the with the production oi densation with the production oi an ethereal retaken from said patent.

action product. The 10110 examples are Example 9 (Example 1 of the patent) .-"conimercial triethanolamine and cocoanut oil, in the proportions of 1 mole of cocoanut oil to 3 molesot trie thanolamine, are heated to a temperature between'about 150 C. and 180 C. for a period 01' about two days. If desired, a current oi inert gas; 'such as dry nitrogen, may be passed through the reaction mixture to speed up the reaction. The resulting product consists formed by the elimination oi amo cule of wa from two molecules or the mono-f y'fl id ester or triethanolamine, with minor proportions of more complex ethers, ethers oi the di-fatty acid ester of triethanolamine, ethers oi the tatty acid esters of triethanolamine wlth-g'lycerin 'or mono or di-glycerides, etc."

. such as di-hydroxypropyl,

' materialshave heated to a temperature C. for ab'out two days i Example 10 (Example 2 of the patent) .The diricinoleic acid ester of trigly e ide-mine is heated to a temperature between about C, and C. for about two days, with-jthe pro"- duction of a product cbnsisting mainly of ethers amine, di-ricinoieate ether, and more complex 'ethers formed by the condensation of more than two molecules, oi

the triglycerylamine diricinoleate, etc. i

Example 11 (Example 3, of the paten'tL-Di ethanolamine monoaeetate is heated toa temperature between about 150 C. and 180 C. for about two days with the production oi a product consisting mainly of the ether of the formula:

cuicoooini It is to be noted'that reference is made to the above co-pending application for patent, now

oinio do our.

(LS, Patent No. 2,293,494, and the last. three cited patents in regard to. afurther elaboration as to various fatty acid esters, i. e., ordinary ve etable oils, fats, and the like, which may be employed. and also as to further description of acceptable hydroiwamines. and polyhydric alcohols which may be employed. It must be recognized that the not losttheir basicitymo any sreat degree, as compared with the hydroxyamines irom which. theymere-originallyderived, Esteriflcation or acylation may tend to reduce the basicity to some degree, although in some'instances it may even be increased, Such moderate changes-areimmateriaiq Generally speaking, it is our preference to obtain the intermediate reactants tronr amines in which there is no hyclrogen atom attached to the amino nitrogen atom. In other words.

use tertiary amines. such triethanolamine. "etc. Generally, speaking, it ,is our preference to prepare the intermediate reactants from the tertiary amines, in which there as ethyl diethanolamine, diethyl ethanolamine, 70 taining substantial amounts of the ether of the is-an alkanolamine radical present, particularly an" ethanolamine radical present. Furthermore, it is our preference to employ-derivatives mainly of'the ethtzr mono-hydroiwpropyl- Schwa'rz, Chemische .Fabrik Diilau.

of glycerol in forming the ether type compound. Particular attention is directed to the types of compounds as prepared according to the directions in the various patents or co-pending application for patent (Patent No. 2,293,494) previously referred to. Incidentally, we desire to point out that T, previously referred to, may represent an RCO radical directly attached to the amino nitrogen radical. In other words, the intermediate reactant may also be an amide. The RCO in such instances may be derived from an acid having less than 8 carbon atoms, or from a detergent-forming acid. However, in such instances the basicity of the amino radical will usually disappear in conversion into an amide; and therefore, in such instances it is usually necessary to have another amino nitrogen atom present which supplies the basicity of the molecule. Such situation is entirely analogous to the presence of an amino nitrogen atom attached to an aryl radical, as in the case of phenyl diethanolamine, previously referred to. There is no objection to any non-basic nitrogen atom contributing part of the molecular weight in the form of an arylamine radical, or in the form of an amido radical, provided that the compound still is basic. due to the presence of some other basic amino ,nitrogen. radical of the kind previously described. J

Attention is again directed to the fact that, although the preceding eleven examples are concemed largely with derivatives of unmodifled. fatty acids, yet the same. procedure is also applicable to modified fatty acid compounds manufactured in the manner previously indicated, to wit, so that such modifications are still convertible into soap or soap-like bodies by agency of suitable alkalies. Similarly, one can prepare compounds of abietic acid, naphthenic acid, or modified forms thereof. It is not necessary to prepare theacylated aminoethers from esters; but if such procedure is desiredythen one can first (prepare esters from naphthenic acid, abietic acid, or the like, which correspond to naturally-occurring esters; for instance, one can prepare naphthenin, abietin, or the like. We particularly prefer to prepare compounds characterized by the presence of at least one. and preferably more than one, hy-

droxy hydrocarbon group in the final product.

Reference is made to the fact that the table appearing in the early part of this application 3 describinga series of representative hydroxy-. aminoethers, contains certain species in which the ether linkage involved combination with a monohydric alcohol. Such alcohols can vary from methyl through octadecyl, or s'tearyl, and may be normal or branched. In view of this fact, it must be appreciated that the scope of the compound contemplated as intermediate reactants in the present application may be derived from hydroxyamine's and monohydric alcohols, as well as hydroxyamines and dihydric' alcohols,.or from} intermolecular reactions of two or, more moles of hydroxyamines. As to the manufacture of such alkyl ethers of hydroxyalkylamines, it is to be noted that they can be manufactured by means of conventional methods now employed, or by methods which involve modification of. previously described methods; or they may be manufactured by the method described in French Patent No. 832,- 288, dated September 23, 1938, to Zschimmerk Having obtained suchalkyl ethers of hydroxyalkylamines by the method suggested in said aforementioned French Patent No. 832,288, or

our preference is to use iatty acids, particularly the fatty acid compounds, such as esters, be-

" cause. they are readily available in the form of naturally occurring oils and fats. Among the various desirable glycerides a". castor oil, olive oil, cottonseed oil, rapeseed oil,. fish oil, menhaden oil, corn oil, cocoanut oil, palm oil, palm kernel oil, linseed oil, sunflowerseed oil, teaseed oil, neats-foot oil, etc. Our preference is that the monomeric chemical compound, exclusive of acyl radicals, shall contain less than 60 carbon atoms, and in most instances, shall contain less than 25 carbon atoms. The acylated aminoethers used in this invention are either mono-or polyamino bodies, i. e., they containone or more amino nitrogen atoms. In all preferred cases, they do not contain more than live such nitrogen atoms, and most preferably, they contain two or three, such nitrogen atoms.

v See also British Patents Nos. 337,774; 306,- 116; and'33'lj737.

Comrmzran Monoxsnrc Dsarvarrvs Example 1 One pound mole of a tertiary ether amine oi the following composition:

obtainable by the action of ethylene oxide on triethanolamine, is reacted with one pound mole of ricinoleic acid, so as to obtain the ester of the following composition:

( :340 CQHIOH) I in which RC0 is the ricinoleyl radical. One pound mole of a product of the kind described under the heading Oxye'thylated glycerol maleate, Example 1" is reacted with one pound mole of a hydroxylated acylated amino ether compound, preferably in the absence of any high boiling hydrocarbon or inert solvent. However, if an inert vaporizing solvent is employed, it is generally necessary to use one which has a higher boiling range than xylene, and sometimes removal of such solvent might present a difllculty. In other instances, however, such Cosrrnsrsn Monousaro Dsarvarrvn Example 2 ing, except that the dimaleate described under the heading "Oxyethylated glycerol maleate, Example 2" is used insteadof the monomaleate.

" moles.

' in the following manner; Anamine COMPLETED Mononmuc DERIVATIVE Example 3 ,The same procedureis followedlas in the two preceding examples, except that the trimaleate is substituted for the monomaleate or dimaleate in the two preceding examples.

COMPLETED Moxouanrc Draw/luvs Example 4 The same procedure is followed as in Examples 2, and 3, immediately preceding, except that for each pound mole of 'the dimaleate, or each pound mole of the trima1eate,.instead of using one pound mole of ether of the kind described in- Example 1, preceding, one employs two pound Comerarrn MONOMERIC Dmuvnrrvr:

Example 5 The same procedure is followed as in Example 3, preceding, except that for each pound mole of trimaleate, instead of addingone pound mole of ether of the kind described. in Example l, preceding, one adds three pound molesof said ether. Couurran Moxomzmc DERIVATIVE Example 6 Reference to the preceding examples will show that in each and every instance oxyethylated glycerol .(ratio' 1 to has been employed as a raw material or primary reactant. In the'present instance, a more highly oxyethylated glycerol is employed; to wit, one involving the ratio of 1 to 18. See Oxyethylated glycerol .maieate, Example 4, preceding.)

COMPLETED Monomsnrc DERIVATIVE Example 7 v 4 Thesame procedure is followed as in Example 6, immediately preceding, except that the oxyethylated glycerol employed represents one'having an even higher degree of oxyethylation. For example, one indicated bythe ratio of l to 21. (See Oxyethylated glycerol maleate', Example 5, preceding.)

COMPLETED Monomeric V Daaxvnrvr: Example 8 diphthalate.

with one mole of dichloroethyl ether is reacted with ricinoleicacid to give the desired, acylated ether.

COMPLETED lvlouousiuc DnarvA-rrva Example 10 The same procedure isflfollowed as' in Examples l-7, preceding, except that the ether is obtained We reaction between ricinoleic acid and an amine of' the following composition.

' OH ClHiOCIH6 -QzHcOH CIHiOH through the mixture. Sometimes it is desirable to add an esteriflcation catalyst, such as sulfuric acid, benzene sulfonic acid, or the like. This is the same general procedure as employed in the manufacture of ethylene 'glycol dihydrogen (See U. S. Patent No. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of aninert solvent, that p v One pound mole of h'ydroxyethyl ethylenediamine is reacted with approximately '5 or 6 pound moles of ethylene oxide to give a diamino type hydroxylated compound. Such compound is reacted with ricinoleic acid and the acylated. ether so obtained is employed in the same manner as indicated by Examples 1-7, preceding, ,except that su'ch ether is used to replace the particular one described in Example 1.

Cougar-ran Mouommrc Dninvs'rrvn Example 9 i I [In the present. instance the same procedure .is followed .as in Examples l-'l, preceding, ex-

cept that instead of employing the acylated ether 55 there described, ,one employs an ether obtained of the following composition 1 NCiHlOCzHaN v canon obtained by the etherization of triethanolam'ine or the treatment .of two moles of diethanolamine This, of course, can be done in any simple man- 0 col.

carries away the water of esterification which mayv be formed, although as is readily appreciated, such water of esterification is absent when such type of reaction involves an acid anhydride, such as maleic anhydride, and a gly- However, if water is formed, for instance when citric acid is employed, then a solvent such as xylene may be presentand employed to carry ofl the water formed. The mixture of xylene vapors and water vapors can be condensed so 'that'the water is separated. The xylene is then returned'to the reaction vessel for further circulation. This is a conventional and well-known procedure and requires no further elaboration.

In the'previous monomeric examples there is a deflnitetendency, in spite of precautions, at,

least in-a number of instances, to obtain polymeric materials and certain cogeneric by-products. This is'typical, of course, of organic ;reactions of this kind, and, as is well known, organic reactions per se are characterized bythe fact that yields are the exception, rather than the 'rule, and that significant yields are satisfactory, especially in those instances where the by products or cogeners may satisfactorily serve with the same purpose as theprincipal or intentional product. This is true inthe present instance. In many cases one is better 01! to ob-' tain apolymer in the sense previously described, particularly .a polymer whose molecular weight is a rather small multiple of the molecular weight of the monomer: for instance, a polymer whose molecular weightis two, three. four, five, or six times the molecular weight of themonomer.

Polymerization is hastened bythe presence of an alkali, and thusin instances where it is necessary to have a maximum yield of the monomer, it may be necessary to take-such precautions, that the alkali used in promoting oxyethylation of glycerol, be'renioved before subsequent reaction.

ner by conversion to sodium chloride, sodium sulfate, or any suitableprocedure.

In the preceding examples of the Completed monomeric derivative, Examples 1 to 10, inclusive, no reference is made to the elimination of such alkaline catalyst, in view of the effectiveness of the low multiple polymers as demulsifiers. Previous reference has been made to the fact that the carboxylic hydrogen atom might be variously replaced by substituents including organic radicals, for instance, the radicals obtained from alcohols, hydroxylated amines, non-hydroxylated amines, polyhydric alcohols, etc. Obviously, the reference is also true, in that a free hydroxyl group may be esterified with a selected acid, varying from such materials as ricinoleic acid to oleic acid, including alcohol acids, such as hydroxyacetic acid, lactic acid, ricinoleic acid and-also polybasic acids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has been previously said as to polymerization, with the suggestion that by-products or 'cogeneric materials were formed, may be rec apitulated with greater definiteness, and one can readily appreciate that the formation of heat-rearranged derivatives or compounds must take place to a greater or lesser degree. Thus, the products herein contemplated may be characterized by being monomers of the type previously described, or esteriflcation polymers, or the heatrearranged derivatives of the same, and thus including theheat-rearranged derivatives of both the polymers and esterification monomers, separately and jointly. Although the class of materials specifically contemplated in this instance is a comparatively small and narrow class of a broad genus, yet it is obviously impossible to present any adequate formula which would contemplate the present series in their complete ramification, except in a manner employed in the hereto appended claims.

Although the products herein described vary so broadly in their characteristics, i. e'., monomers through sub-resinous polymers, soluble products,

water-emulsifiable oils or compounds, hydrotropic 4) materials, balsams, sub-resinous materials. semiresinous materials, and the like, yet there is always present the characteristic unitary hydrophile structure related back to the oxyalkylation, particularly the oxyethylation of theg ycerol used as the raw material. When employed as a demulsifier in the resolution of oil field emulsions, they may be added to the emulsion at the ratio of 1 part in 10,000, 1 part in 20,000. 1 part in 30,000, or forflthat matter, 1 part in 40,000. In such ratios it well may be that one can not differentiate between the solubility of a compound complete y soluble in water in any ratio, and a semi-resinous product apparently insoluble in water in ratios by which ordinary insoluble materials are characterized. However, at such ratios the importance must reside in interfacial position and the .ability to usurp, preempt, or replace the interfacial position previously occupied perhaps by the emulsifying colloid. In any event, reviewed in this light, the. obvious common property running through the entire series, notwithstanding var-. iation inmolecular size and physical make-unis absolutely apparent. Suchstatement is .an obvious, over-simplification or the rationale underlying demulsification, and does not even consider the resistance of an interfacial film to crumbling, displacement, being forced intosolution, altered wetability and the like. As to amidiiication polymers, for instance, where Z is a polyamino amide radical, see what is said subsequently.

MoNoMEaIo DEsIvATIvEs .Ixcmnmc HEAT-REARRANGED Coosmms Example 1 COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Example 2 The same procedure is followed as in the preceding example, except that polymerization is continued, using either a somewhat longer reaction time, or it may be a somewhat higher temperature, or both, so as to obtain ,a material having a molecular weight of approximately threeto four times that of the initial product.

COMPLETED POLYMERIC DERIVATIVES INCLUDING HEAT-REARRANGED CIOGENERS Esgample-t' The same procedure is followed as in Examples .1 and 2, preceding, except that one employs as a reactant one of the polyamino ethers instead of one of the mo'noamino ethers.

COMILETED POLYMERIC. DERIVATIVES INCLUDING HEAT-REARRANGED COGENERS Courtaran Example 4 The same procedure is followed as in Examples 1 to 3, preceding, except that one polymerizes a mixture instead of a single monomer, for instance, a mixture of materials of the kind described in Completed monomeric derivative, Example 3, and in Completed monomeric derivative. Example 4, are mixed in molecular proportion and subjected to polymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not be obtained as a result ofa twostep procedure. In other words, one need not convert. the reactants into the monomer and then subsequently convert the monomer into the polymer. The reactants may be converted through the monomer to the polymer in one step. Indeed, the formation of the monomer and polymerization may. take place simultaneously. This is especially true if polymerization is conducted in the absence of a liquid such as xylene, as previously described, and if one uses a comparatively higher temperature, for instance, approximate- .iy 200 0., for polymerization. Thus, one pound mole of oxyethylated glycerol polymaleate of the kind described is mixed with one pound mole of Such mixture is reacted for approximately 20 oncim neous. It is stirred constantly during reaction. Polyfunctionality may reside in dehydration (etherization) oftwo hydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be made in a single step, iilustrates a phenomenon which sometimes occurs either in such instances where alcoholicbodies of the kind herein illustrated are contemplated as reactants, or. where somewhat kindred alcoholic bodies are employed. The reactants may be mixed mechanically to give a homogeneous mixture, or if the reactants do not-mix to give a homogeneous mixture, then early in the reaction stage there is formed, to a greater or. lesser de-' gree, sufilcient monomeric materials so that a homogeneous system is present. Subsequently, as reaction continues, the system may become heterogeneous and exist in two distinct phases, one being possibly an oily body of moderate viscosity, and the other being a heavier material, which is sticky or sub-resinous in nature. In many instances it will be found that the thinner liquid material is -a monomer and the more viscous or resinous material is a polymer, as previously described. Such product can be used for demulsification by adding a solvent which will mutually dissolve the two materials, or else, by separating the two heterogeneous phases and employing each as if it were a separate product of reaction.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water; petroleum hydrocarbons such as gasoline, kerosene, stove oil, a coal tar product such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured, alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials herein described, may be admixed with one or more of the solvents customarily used in connection with conventional agents. i It is well-known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water-solubility. Sometimes they maybe used in a form which exhibits relatively limited oil-solubility. However, since such reagents are 'sometimesused' in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is'not significant, be cause said reagentsundoubtedly have solubility within the concentration employed. This .same

fact is true'in regard to the material or materials I herein described, except that they are invariably water-soluble. 1

Wedesire to point out that the superiority of the reagent or demulsifying agent used in our herein described process for breaking petroleum 2,353,703 hours at about 200. c. until the mass is homoge available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are-concerned:v but we have found that such a demulsitying agent has commercial value, as it will eco- .nomlcally break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulsifying agents heretofore available.

In practicing our improved process for resolving petroleum emulsions of the water-in-oil. type, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now generally used to resolve or break petroleum emulsions with a chemical reagent, the above, procedure being used either alone, or in combination with other demulsifying procedure,

such as the electrical dehydration-process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their' emergence. This particular type of application ,is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

cognizance must be taken of the fact that the surface of the reacting vessel may increase or decrease reaction rate and degree of polymerization, for instance, an iron reaction vessel speeds up reaction'and polymerization, compared with a glass-lined vessel.

As has been previously indicated, 'the subgenus employed as an alcohol in the present instance is one of a series of alcoholic compounds which are contemplated in our co-pending applications Serial Nos. 447,151; 447,152; 447,153; 447,154; 447,155; 447,156; 447,157; 447,158; 447,159; 447,161'; 447,162; 447,163; 447,164; 447,-' 165; 447,166; 447,167; and 447,168, filed June 15, 1942.

It is to be noted that in such instances where the alcoholic body contains a reactive amino hydrogen atom, for instance, in the case where an acylated hydroxylated polyamine is employed,

. stances, the expression esterification polymers emulsions, is based upon its ability to treat cer-' tain emulsions more'advantageously and at a somewhat lower cost than is possible with other, 76

is the appended claims, includes amidification polymers, as well as esteriflcation polymers.

Having thus described our invention, what we aclaimqasnew and desire. to secure by Letters I Patent is: v 1. A process for. breaking petroleum emulsions-of the waterein-oil type, characterized by subjecting theemulsion totheaction of a demulsifier-comprising amember of the class consisting of monomers, sub-resinous esterification polymers, andcogenericsub-resinous heat-rearranged-derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(ctH,..o)..'oocmcoozw' in which R is the carboxyl-free radical of a polybasic carboxy acid having not over 8 carbon atoms; R1 is a hydroxylated acylated aminoether radical, said radical containing (a) at least one amino nitrogen atom free from attached aryl and amide-linked acyl radical; (b) said radical containing at least one basic hydroxyamine radical ether-linked to at least one radical selected from the class of glycerol radicals, polyglycerol radicals, glycol radicals, poly glycol radicals, basic hydroxyamine radicals, amidohydroxyamine radicals and aryl alkanolamine radicals, said basic hydroxyaminoether radicals being characterized by containing not over 60 carbon atoms; said hydroxylated acylated amino radical containing a detergent-forming monocarboxy acid radical having at least 8 carbon atoms and not over 32 carbon atoms; and said aforementioned acyl radical being a substituent for a hydrogen atom of the alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 2 to 4; n represents the numerals 3 to n" represents the numerals 1 to 2; :1: represents the numerals 0 to 2; y represents the numerals 0 to 2; 2 represents the numerals l to 3; 2: represents the numerals 0 to 1; and y represents the numerals 1 to 2.

2. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

- the class of glycerol radicals, polyglycerol radicals, glycol radicals, polyglycol radicals, basic hydroxyamine radicals, amidohydroxyamine radicals and aryl alkanolamine radicals; said basic hydroxyaminoether radicals being characterized by containing not over 60 carbon atoms; (0) said hydroxylated acylated amino radical containing a detergent-forming monocarboxy acid radical having at least 8 carbon atoms and not over 32 carbon atoms; and said aforementioned acyl radical being a substituent for a hydrogen atom of an alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 2 to 4; n represents the numerals 3 to 10; :trepresents the numerals 0 to 2; y represents the numerals 0 to 2; andz represents the numerals 1 to 3.

atoms; R1 is a hydroxylated acylated aminoether radical, said radical containing (a) at least one 7 amino nitrogen atom free from attached aryl and amido-linked acyl radical; (b) said radical containing at least one basic hydroxyamine radical ether-linked to at .least one'radical selected from the class of glycerol radicals, polyglycerol radicals, glycol radicals, polyglycol radicals, basic hydroxyar'nine radicals, amidohydroxyamine radicals and aryl alkanolamine radicals; said basic hydroxyaminoether radicals being characterized by containing not over 60 carbon atoms; (0) said hydroxylated acylated amino radical containing a detergent-forming monocarboxy acid radical having at least 8' carbon atoms and not over 32 carbon atoms; and said aforementioned acyl radical being a substituent for a hydrogen atom of an alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; 12' represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 2! represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a polar member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heat-rearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

l(oimo).. oocaoooz in which R. is a carboxyl-free radical of a dibasic carboxy acid having not over 6 carbon atoms; R1 is a hydroxylated acylated aminoether radical, said radical containing (a) at least one amino nitrogen atom free from attached aryl and amido-linked acyl radical: (b) said radical containing at least one basic hydroxyamine radical ether-linked to at least one radical selected from the class of glycerol radicals, polyglycerol radicals, glycol radicals, polyglycol radicals, basic hydroxyamine radicals, amidohydroxyamine radicals and aryl alkanolamine radicals; said basic hydroxy aminoether radicals being characterized by containing not over 60 carbon atoms; (0) said hydroxylated acylated amino radical containing a detergent-forming monocarboxy acid radical having. at least 8 carbon atoms and not over 32 carbon atoms; and said aforementioned acyl radical being a substituent for a hydrogen atom of an alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 1 represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

. in which R is a carbonyl-free radical of a, dibasic car-boxy acid having not over 6 carbon atoms; R1 is a hydronylated acylated aminoether radical, said radical containing (a) at least one amino nitrogen atom free xrpm attached aryl and amido ilinked acyl radical; (11) said radical containing: at least one basic hydroxyamine radical ether-linked to at least one radical selected. from the class of glycerol radicals, polyglycerol radicals, glycol radicals, polyglycol radicals, basic hydroxyamine radicals, amidohydroxyamine. radicals and aryl allranolamine radicals; said basic hydroxyaminoether radicals being characterized by containing not overfiil carbon atoms; (c) said hydroiiylated acylated amino radical containing a detergent-forming monocarboxy acid radical having at least 8 carbon atoms and not over 32 carbon atoms; and said aforementioned acyl radical being a substltuent for a hydrogen atom of an alcoholic hydroxyl radical; Z is an acidic hydrogen atom equivalent including the acidic hydrogen atom itself; n represents the'nu-merals 3 to 10; :1: represents the numerals to 2; y represents the numerals (l to 2; and 2 represents the numerals l to 3.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by sub-.

jecting the emulsion to the action of a demulsifier comprising a polar acidic member of the class consisting of monomers, sub-resinous esteriflcation polymers, and cogeneric sub=resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(Cirnon'oo'olaoooz z CaH50a[(CaH40)"'H],

[(onrlowoooRcooima in which R is a carb'oxyl-free radical of a dibasic carbox acid having not over 6 carbon atoms; R1 is a hydroxylated acylated aminoether radical, said radical containing (a) at least one amino nitrogen atom free from attached aryl and, amide-linked acyl radical; (b) said radical containing at least one basic hydroxyamine radical ether-linked to atleast one radical'selected from the class of glycerol radicals, polyg'lycerol radicals, glycol radicals, plyglycol radicals, basic hydroxyamine radicals, amidohydroxyamine radicals and aryl alkanolamine radicals; said basic hydroxyaminoether radicals being characterized by containing not over 60 carbon atoms; (c) said hydroxylated' acylated amino radical containing a higher fatty acid radical having at least 8 and not over 32 carbon atoms; and said aforementioned acyl radical being a substituent for a hy-' drogen atom of an alcoholic hydroxyl radical; Z

' is an acidic hydrogen atom equivalent including the acid hydrogen atom itself; n represents the numerals 3' to 10; :c represents the numerals 0 to 7. A. process for breakingpetroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsh tier comprising a polar acidic member of the amido-linked acyl radical; (b) said radical containing at least one basic hydroxyamine radical ether-linked to at least one radical selected from the class of glycerol radicals, polyglycerol radicals, glycol radi'cals,'polyglycol radicals, basic hydroxyamine radicals, amidohydroxyamine radicals and aryl ,alkanolamine radicals; said basic hydroxyarninoether radicals being characterized by containing not over carbon atoms;

(0) said hydroxylated acylated amino'radical containing a, higher fatty acid radical having 18 carbon atoms; and said aforementioned acyl radical being a substituent for a hydrogen atom 8. A process for breaking petroleum emulsions of the water-in-oil'type, characterized by subiecting the emulsion to the action of a demulsiher comprising a'poiar acidic member of the class consisting of monomers, sub-resinous esterification polymers, and cogeneric sub-resinous heatrearranged derivatives of the monomers and aforementioned polymers, separately and jointly, and of the following formula:

[(oiEno),.'oooRoooz]z C3HlO3 [(CH40 n H] uoimoin'oo'oneooml, inwhichR is a carboxyl-free radical of a dibasic carboxy' acid having not over 6 carbon atoms; R1 is a hydroxylated acylated aminoether radical, said radical containing (a) at least one amino nitrogen atom free from attached aryl'and ar'nidolinked acyl radical; (b) said radical containing at least one basic hydroxyamine radical etherlinked to at least one radical selected from the class of glycerol radicals, polyglycerol radicals,

glycol radicals, polyglycol radicals basic hydro'xwamine radicals, amidohydroxyamine radicals and -aryl alkanolamine radicals; saidbasic hydroxyaminoether radicals being characterized by containing'not overfiO carbon atoms; (0) said bydroxylated acylated amino radical containing a ricinoleyl radical; andsaid aforementioned acyl 2; 1/ represents the numeral 0 to 2; ands-rep resents the numerals l to 3.

radicalbeing a substituent for a hydrogen atom of an alcoholic hydroxyl radical; Z isan acidic 'hydrogen atom equivalent including the acidic hydrogen, atomv itself; 1; represents the numerals 3 to 10;, r represents the'nuineralsil to 2; y represents the numerals 0 to 2; and zrepresent's the numerals 1 to 3. g f V MELVIN DE GROOTE.

BERNI'MRD KEISER. 

